New insoluble monazo compounds



F'atented May 12, 1942 2,282,379 NEW INSOLUBLE MONAZO COMPOUNDS Maurice Arthur Thorold Rogers and Wilfred Archibald Sexton, Blackley, Manchester, England, assignors to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Original application June 22, 1938,

Serial No. 215,268. Divided and this application January 28, 1941, Serial No. 376,334. In Great Britain June 23, 1937 7 Claims.

This invention relates to new water-insoluble monazo compounds which comprise as one component the radical of an arylene-thiazyl-methyl ketone of the benzene or naphthalene series and as the other component the radical of a diazotized arylamine which is devoid of water-solubilizing groups, such as sulfonic acid and carboxyl and especially to new azo dyes and to fibers dyed with the new compounds. More particularly the coupling components of the new compounds are represented in general by the formula in which Ar stands for an ortho-arylene radical of the benzene or naphthalene series which may or may not be substituted, but if substituted it may not carry groups inducing solubility in water, such as carboxylic or sulfonicacid groups. The symbol represents an acyl radical of the aliphatic or aromatic series, such as acetyl, benzoyl and nitro-benzoyl.

The new insoluble azo compounds are obtained by coupling a diazotized arylamine which is devoid of groups inducing solubility in water with the above-identified coupling components, the coupling being carried out so that the azo compound is formed either in substance or on a substratum such as cotton fiber. The colors thus obtained are insoluble compounds having yellow to orange shades and good fastness properties.

The invention will be more fully set forth in the following more detailed description which includes examples that are given as illustrative embodiments of the invention and not as limitations thereof. Parts are expressed in parts by weight unless otherwise noted.

Example I 10 parts of acetonyl-benzthiazole are mixed with 20 parts of Turkey red oil, 250 parts of boiling water are added, followed by 20 parts of aqueous caustic soda 60 Tw. The clear solution is diluted with cold water to make 1000 parts by volume.

Cotton cloth is impregnated with the above solution, dried, and developed by immersion in a bath made as follows: r

10 parts of 4-chloro-2-methyl-ani1ine hydrochloride are dissolved in 200 parts of cold water containing 10 parts of hydrochloric acid32" Tw.

The solution is cooled to 12 C. and 4 parts of sodium nitrite dissolved in 20 parts of cold water are slowly added.

After standing for 30 minutes the solution is made neutral to Congo red indicator paper by the addition of about 7.5 parts of sodium acetate dissolved in 15 parts of cold water.

10 parts of acetic acid 50% are then added and the solution diluted with 750 parts of water.

After development the fabric is rinsed in cold water, soaped at the boil, rinsed and dried. The cotton was dyed a bright greenish-yellow shade which had moderate to good general fastness properties, being unusually fast to chlorine and to soda-kier-boiling.

The compound is represented by the formula II to XXVI are the general fastness properties, i V benzene series. namely fastness to light, washing,chlorine and l. 4. A compound in accordance with claim 1 soda-kier-boiling. in which the second component is a 2-acetonyl- A preferred type is that in which the ortho- 30 benzthiazole. j arylene radical of the coupling component is 5. The compound represented by the formula from the benzene series and the acyl radical is r j sented by the formula r N\ 7. The compound represented by the formula X-NHg Ar OOHz- --R p on, A

. 01 6A N I V g s 7 l, CO-NHQ. in which XNH2 is'a primary arylamine of the N=Nc 1-o v V 1 benzene series which is devoid of groups which H S/ induce solubility in water; Ar is an ortho-arylene I radical of the group consisting of the benzene and naphthalene series which are devoid 013.55 groups which induce solubility in water; and MAURICE ARTHUR THOROLD ROGERS. V

--COR is an acyl group. WILFRED ARCHIBALD SEXTON.

that were made similarly to the process de- 2. A compound in accordance with claim 1 scribed in Example I except that different comin which R is CH3. ponents were used. 3. A compound in accordance with claim 1 Coupling component Diazo component Shade Fastness 2-acetonyl-benz-thiazole fi-chloro-zamino-toluene Greenish yellow-" Moderate. 7 4-chloro-2-amino-anisole. Red yel1ow Fairly good eetonyl-alpha-naphtho-thiazole 4-chloro-2-amino-anisole do 00d. dn 4-benzoy1-amino-2, fi-diet Novel orange Moderate fi chloro-4*methy1-2-acetonyl-benz-thiazole 4-chIoro-2-amino-aniso1e Red ye11ow ood. -do 2-oh1oro-aniline Green yellow Do. 3-ch1oro-ani1ine do. Do. 2, -dich1oro-ani1ine do Do. 5-ch1oro-2-amino-t01uene -.do Do. 4-chloro-2-amino-aniso1e Greenish yellow." 1 Do. 2-ch1oro-aniline Green yellow Do. 3-ch1oro-aniline do Do. 2, 5-dich1oro-aniline do Do. 5-chloro-2-amino-toluene. D0. 4-chloro-2-amino-anisole Dull yellow- Moderate. Z-chloro-aniline 7 00d. 3-chloro-aniline d Do. 2, 5-diehloro-aniline D0. 5-chloro-2amino-to1uen .v Do. Zqhlmfo-anilinn D0, 3-ch1oro-aniline Do. B-chloro-nnilin Do. 6-c1 i1oro-2-acetonyl-benz-thiazole 6-ehloro-2-amino-to1uene Do. 2-acetonyl-benz-thiazole-5-carboxy1ic acid-anilide 2-chloro-aniline Very good.

do 5-ch1oro-2-ami no-t01uene do D0.

The fastness properties indicated in Examples in which Aris an ortho-arylene radical of the OH acetyl. In this type there is a desirable uni- CH: E l a formityof fastness properties. 1 i I O=O N i This application is a division of our applicac 7 1 tion Serial No. 215,268, Patent 2,233,873, issued I C1 March 4, 19,41. 7 Y I v 'From the foregoing disclosure it will be r I recognized that the invention is susceptible of r The Compound represented by t formula,

modificationwithout departing from the spirit 40 CH and scope thereof and it is to be understood a that .the invention is not restricted to the specific 1 illustrations thereof herein set forth. I o 7 We claim: H OC2Ha 1. A water-insoluble azo compound repre- (31 s CERTIFICATE OF CORRECTI ofi. Patent No. 2,2 2,579 May 12., 19mg MAURICE ARTHUR THOROLD ROGERS, ET AL.,

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, line 9, in the t'ab1e, for 5-chloro' read 6-ch1oro-; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 2lst'day of July, A. D 19L 2.

Henry Van Arsdale, (Seal) Acting Commissioner of Patents. 

